Detergent and wetting compositions



all 2 ambie Ohio, a corporation of Ohio No Drawing. application June 13, 1935, No. 26,519

My invention relates to new and improved laundering preparations which have excellent wetting, sudsing and detergent properties especially in hard water.

Esssentially my invention comprises, as a detergent, a mixture of water-soluble salts of the product of the reaction of a sulfating agent on higher molecular weight normal primary aliphatic alcohols under conditions favoring the formation of the sulfuric acid ester and water-soluble salts of true sulfonic acids described below, and also comprises the process of producing said detergents. to sulionate promoters is to be interpreted to mean the salts of the true sulfonic acids more specifically set forth hereinafter, and reference to aikyl sulfates" is to be interpreted to mean the salts of the above noted reaction products derived either from individual higher molecular weight alcohols or from a mixture of such alcohols, such as may be obtained by the reduction of natural fats and fatty oils. It should be noted that the term "alkyl sulfate as above defined includes those sulfuric acid ester salts containing small amounts of salts of true sulfonic acids unavoidably formed under the conditions of sulfation of the alcohols.

It is an object of my invention to improve sudsing and detergent properties of the water-soluble salts of primary alkyl sulfuric acids having eight or more, especially eight to eighteen, carbon atoms in the molecule. These alkyl sulfuric acids have the general formula RHSO4 where R is an alkyl radical containing preferably eight to eighteen carbon atoms. The most commonly used water-soluble salts of these alkyl sulfuric acids are those of the alkali metals, ammonia, substituted ammonia, and organic bases, but other water-soluble salts come within the scope of 11m invention. Further objects and advantages will become apparent in the course of the following description.

I have noted that alkyl sulfates, although good sudsing agents in distilled water, are somewhat less emcient in these respects when used in the average type of hard water, especially in the presence of soiled fabrics. I have found, for example, that in natural hard water equivalent in hardness to 21 grains CaCOa per U. 8. gallon, especially when the calcium compounds predominate over the magnesium the detergent power is less than in soft water and the sudsing power, particularly the suds stability, is markedly reduced, especially in the presence-of soiled fabrics. Since detergent and sudsing power and suds stability are properties of primary consideration in the choice of an efficient detergent in common laundering operations, I have directed efforts to improve said properties.

I have found that the above difliculties in suds- Reference in the specification and claims ing and detergent properties may be overcome and that wetting, sudsing and detergent agents of improved emciency, in various forms, such as for example flaked, spray or drum dried, pufl'ed. powdered, shredded, paste, liquid, or other form, may be obtained by adding to or incorporating with known water-soluble alkyl sulfate detergents, a small amount of a water-soluble salt of a true alkyl sulfonic acid corresponding to the general formula MO-JK-Ri-SOi-OH, in which R, denotes an aliphatic radical-having at least eight carbon atoms, especially eight to eighteen carbon atoms, XR.'1 denotes an oxyalkylene (-O R1) or an amino alkylene radical. (The term "alkylene radical" is used herein with its accepted meaning: an aliphatic radical having two unattached valences.)

The alkyl sulfate detergents may be obtained byneutralization, with a suitable base such as sodium or potassium hydroxide, ammonia, an amine or an organic base, of the reaction product of normal primary alcohols, such as those obtainable by reduction of fatty acids, or oils and fats of vegetable or animal origin, with a sulfating agent such as sulfuric acid, chlorsulfonic acid and the like in the customary manner wherein the alcohol is substantially completely sulfated.

The true sulfonates, which act as promoters for improved sudsing and detergent power, are obtainable, for example, by the condensation of fatty acids of vegetable or animal origin, or their synthetic equivalents, or their derivatives, with hydroxylated or halogenated derivatives of ethyl sulfonic acid or of ethionic acid, carbyl sulfate or amino sulfonic acid, or corresponding derivatives prepared from glycerin, such as 1,2 dihydroxy propyl 3 sulfonic acid or salts of these sulfonated compounds.

The following materials are illustrative of the types of suifonate promoters operative in the practice of my invention.

(Sodium salt of the oleyl acid amide of methyl me) CHi(CH CH=CH(CHl)1C-0CHrGH1SO|NH4 (Oleic acid ester of ammonium isetbionate) RCZO:CHQ CHOHOHISOJNB v wherein R denotes an aliphatic radical such as that present in lauric, oleic, myristic, stearic acids or the mixed acids obtainable from coconut or palm kernel oils or talow. (Coconut oil fatty acid ester of sodium glyceryi sulfonate, for example.)

Thus it will be seen that in the general formulas, the R1 grouping may have either two or three carbon atoms in the molecule. Of course,

other soluble salts of these types of compounds, in addition to those specifically given above, may be used in the practice of my invention.

lhe su'lfonate promoters themselves in aqueous solution possess sudsing and cleansing power, even in hard water, but their value as promoters lies in the remarkable fact that when such a compound is added to a water-saluble salt of a sulfated higher alcohol the mixture possesses sudsing and detergent power far in excess of expectations based upon the behavior of the components of the mixture when used separately. In other words, the sulfonate promoter is much more than additive in its effect.

The amount of sulfonate promoter which is to be used, as well as the magnitude of the effect produced thereby, depends upon many factors,

such as the nature of the sulfonate promoter, the nature of the alkyl sulfate, and the conditions under which the product is used. Even small additions of any of the sulfonate promoters mentioned produce an effect which is greater than can be predicted from the properties of the sulfonate promoter alone. The optimum effect is generally obtained by the replacement of about five to about thirty per cent of the alkyl sulfate with a sulfonate promoter. I have found that in excess of thirty per cent, for example sixty percent, may be used and that the effect will still be beneficial but not much greater than would be predicted upon the basis of the behavior of the constituents when used alone.

The method of adding the sulfonate promoter to the alkyl sulfate to improve and stabilize sudsing and to improve detergency may vary considerably. For example, the sulfonate promoter may be added in dry form to alkyl sulfate paste and incorporated therein by any of a number of well known methods. The mixture may be used in paste form or may be dried in any manner such as for example spray drying or drum drying to give it a variety of forms. In the improvement of liquid detergents, the sulfonate promoter may be dissolved therein before use.

In the preparation of products of solid or extruded form, the sulfonate promoter may be added to the solid alkyl sulfate and incorporated 2,1 cases The relative sudsing power of certain mixtures was determined by shaking a definite quantity of solution containing the detergent mixture under standardized conditions for a definite period of time and noting the volume of suds formed. The stability of the suds formed was also noted. The detergency tests were made on uniformly soiled fabric according to a standardized procedure known to give comparative results.

Example 1.-In this example, commercial sodium alkyl sulfate, prepared from the alcohols obtained from coconut oil by high pressure hydrogenation, and having the following approximate analysis, was employed: 48 per cent actual sodium alkyl sulfate, 48 per cent sodium sulfate, 2 per cent unsulfated material, 1 per cent moisture and 1 per cent sodium chloride. The sulfonate promoter consisted of commercial sodium salt of oleic acid amide of methyl taurine containing approximately 33 per cent actual sulfonate, 64 per cent sodium chloride, and 3 per cent sodium sulfate. A mixture containing the dry active ingredients in the ratio of 9 parts actual alkyl sulfate to 1 part of actual oleic acid amide -of methyl taurine was prepared. Likewise, mixtures were prepared containing the active detergents in the ratio of 8:2 and 7:3. Separate solutions were prepared from each of the above mixtures and the individual constituents thereof. The water used contained compounds of calcium and magnesium in the molar ratio of 2.9 calcium to 1 magnesium, the total hardness of the water being equivalent to 21 grains of CaCOa per U. S. gallon. The concentration of actual detergent was the same, and equal to that of a 0.10 per cent solution of the alkyl sulfate (per cent solids basis). It will be noted that the amount of active ingredients present was approximately 0.048 per cent. c. c. of the solutions at 85-90 F. were poured into suitable 500 c. c. graduated cylinders and were shaken for 20 seconds in a shaking rig, after which the volume of the suds formed was noted. The cylinders were allowed to stand for 5 minutes, after which period the volume of suds was again noted. The data obtained are given in the following table.

Table I Experimental Predicted result Percent actual de- Descrlption of sample tergent in Cc. suds Cc. suds solution after after Suds ior- Suds stashaking standing motion bility 20 sec. 5 min.

Sodium alkyl sulfate (48% actual) (A) 0. 048 H0 30 Sullonete promoter (33% actual) (B) .048 200 185 Mixture of A+il contg. the actual detergents in the proportion of 9:1 048 120 115 33 ixture of A+li cont tl proportion of 8:2 048 150 121 36 Mixture of A+B contg he actual detergents in the proportion of 7:3 048 250 50 127 40 The exceptionally useful and unpredictable therein by any process for accomplishing the desired homogenization, such as the well known milling process in the soap industry. The mixture of detergents may then be formed into a product having any desired physical shape.

The sudsing and detergent power of mixtures coming within the scope of my invention are illustrated in the following examples which include data taken from actual tests carried out both-in the absence and presence of standard soiled fabrics.

more-than-additive effect of the sulfonated promoter on the sudsing of the alkyl sulfate in hard water is thus shown. Even more remarkable is the improvement in the stability of the suds noted under identical testing conditions. Other primary alkyl sulfate detergents and sulfonate promoters described herein may be substituted in the above test with similar results.

The results of other experimental work carried out under comparable conditions indicated that the amounts of inorganic salts such as sodium sulfate or sodium chloride commonly occurring in commercial products, within rather wide variations, had but little effect on either the amount and stability of the suds or the detergency of the products, provided of course equal quantities of actual detergents were used. A certain amount of the inorganic sulfate salt naturally and unavoidably occurs in the neutralized product as made commercially.

Example 2.-Separate solutions of commercial sodium alkyl sulfate produced from the alcohols obtainable from coconut oil by sodium reduction and containing about 48 per cent actual detergent, and of commercial oleic acid ester of ammonium isethionate containing approximately 49 per cent actual sulfonate promoter, were'prepared. These solutions were mixed in the necessary proportion to yield a solution containingthe active ingredients in the proportion 80 parts of actual sodium alkyl sulfate to 20 parts actual sulfonate promoter. Testsolutions containing 0.10 per cent solid material or about 0.048 per cent actual detergent were then prepared from the sulfonate promoter, the alkyl sulfate, and the mixture of alkyl sulfate and sulfonate promoter detergents. Sudsing tests were carried out as above, the temperature of the test being -90 F. and the hardness of the water being 21 grains per gallon as described above. It will be seen that the mixture of detergents was markedly superior to either of the individual constituents both in amount of suds and in the stability of suds.

it will be noted, is slightly better than the other in sudsing characteristics. It is clearly'shown, however, that the mixing of the alkyl sulfate and suli'onate promoter produces a particularly new and exceptionally useful morathan-additive effect not predictable from the properties of the individual ingredients themselves. In fact, in general eflect, the mixture was superior to either of the individual constituents.

It is understood, of course, thee it is not necessary to form an intimate mixture of the materials such as would be obtained by thoroughly mixing pastes or concentrated solutions of the respective constituents. A mechanical mixture of the dry ingredients in proper proportion may be used with identical results. Similarly, the materials may be added individually to the water in the correct proportion to effect similar improvements in the sudsing qualities of the alkyl sulfate. The manner of mixing is not a limitation of my invention.

The sudsing properties of alkyl sulfates of other alcohols can be similarly improved by the addition of any of the above mentioned sulfonate' promoters, but obviously because of the variable solubility of the alkyl sulfates of the various alcohols the optimum results will vary according to the conditions of use.

In the determination of the suitability of mateials as washing agents, it is found that volume of suds produced, stability or lasting quality of the suds, and cleansing or detergent power, are three diflerent properties which are not neces- Table II I Experimental Predicted result S5? Descri tion oi sum is ac Casuds 0c. suds p p 23 332 alter Sudsjior- Brad? stashaking s ng ma on t 20 sec. 5 min. y

Alkyl sulfate (48% actual) (A) 0. 048 35 Sultanate promoter (49% actual) (B) 049 110 Mixture of A+B contg. the actual detergents in the proportion of 8:2 048 350 325 112 41 Example 3.-The coconut oil fatty acid ester of sodium glyceryl sulfonate used as promoter in this example contained about 85 percent actual sulfonate promoter and the alkyl sulfate detergent was similar in composition to that used in the previous examples. Sudsing tests were carried out as in the case of Example 2. The improvement both in sudsing and in the stability of suds is convincingly demonstrated in the following table.

sarily associated with each other, but which are all desirable in a good washing agent. Good sudsing or stability of suds in clear water, furthermore, is not necessarily followed by good sudsing, or especially by good stability of suds, in the presence of soiled fabrics.

The improvement in sudsing properties of the alkyl sulfate detergents hi the presence of standard soiled fabric and the improvement in the detergent properties of same by the addition of Table III Experimental Predicted result est Description of sample ac Cc. suds Cc. suds $33 after after Buds ior- Buds mshaking standing mation bllity 20 sec. 5 min.

Alkyl sulfate (48% actual) (A) 0. 048 no 2; Sulionate promoter (85% actual) (B) .051 125 Mixture of A+B contg. the actual detergents in the proportion of 9 l .048 115 ill 27 Mixture of A+B contg. the actual detergents in the proportion of 8:2 048 260 250 113 30 In all of the above examples it will be noted that the amount of suds and the stability of the suds obtained by shaking a solution of the mixed detergents is not predictable. One detergent,

the above sulfonate promoters is illustrated in the following example.

Example 4.The materials used were as follows: (A) a commercial detergent product having the following approximate analysis: 46.5 per cent of the sodium salt of alkyl sulfuric acid prepared from the alcohols obtainable from coconut oil, 52.2 per cent sodium sulfate and. 1.3 per cent petroleum ether extract; (B) a commercial form of the sodium salt of oleyl acid amide of methyl taurine, and consisting approximately of 33 per cent of actual sulfonate, 64 per cent sodium chloride and 3 per cent sodium sulfate.

Mixtures of the above compounds containing: first, 90 per cent of (A) and 10 per cent of (B), and second, 80 per cent (A) and per cent (B) were prepared by mechanically mixing the correctly proportioned ingredients. It will be noted that in these two mixtures the actual detergent ingredients were in the ratio of 12.7:1 and 5.6:1, respectively. Solutions of 21 grain water as previously described containing various percentages of the mixtures were prepared and used in the washing of uniformly soiled fabric at 100 F. according to a standardized procedure known to give comparative results, to show the amount of detergent required to obtain a given degree of whiteness. sudsing data were also collected during the washing tests. Concentrations of the respective actual detergents necessary to wash the fabric under identical conditions to a given degree of whiteness as measured by an electrical grading apparatus not dependent on human eye comparisons were as follows.

Table IV Predicted result- Percent actual detergent in solution to give same whiteness Experimental- Percent actual detergent in solution to give same whiteness Description of sample Alkyl sulfate (46.5% actual) (A 0.033 Sulionete promoter (33.0%

actual) (B) 0. 012 Mixture of A-i-B contg. the actual detergents in ratio of 12.711 0. 020 029 Mixture of A+B contg. the actual detergents in ratio 015.621 0. 020 026 A comparison of the experimental and predicted data will readily show the marked improvement in detergency and especially the more-than-additive effect obtained by the addition of the sulfonate promoter to the alkyl sulfate in that less of the mixture is required to give a definite degree of whiteness than that predictable from the properties of the individual constituents of the mixture.

The concentrations of the respective actual detergents necessary to yield a. given amount of suds in the presence of soiled fabrics were as follows.

The results in Table V show clearly the morethan-additive sudsing effect produced by the addition of a sulfonate detergent of the character above described to a sulfate detergent, and demonstrates that a smaller quantity of the mixture is required to give a definite volume of suds than that predictable from the properties of the individual constituents of the mixture. Similar results are obtained if other sulfonate promoters such as the oleic acid ester of ammonium isethionate or the esters of sodium glyceryl sulfonate are used.

In the tabulated data above, I have presented what I term experimental and predicted results to show the marked more-than-additiveeffect in sudsing and detergent power noted when the respective detergents are mixed with each other as herein described. The experimental data are the results of actual tests, while the predicted results on the mixtures are calculated mathematically from the experimental data ob tained on the individual constituents.

In the claims, reference to coconut oil is meant to include that group of tropical nut oils which are of similar chemical constitution, in general, and for use in my products are substantially interchangeable and of which coconut oil and palm kernel oil are the best known members.

Having thus described my invention, what I claim as new and useful and desire to secure by Letters Patent is:

1. A wetting, sudsing and detergent agent comprising a mixture of a water soluble alkyl sulfate having eight to eighteen carbon atoms in the alkyl radical and a water-soluble salt of a true sulfonic acid corresponding to the general formula in which R denotes an aliphatic radical having eight to eighteen carbon atoms, and X-R1 denotes an oxyalkylene or an amino alkylene radical, the ratio of true sulfonate to alkyl sulfate being not greater than three to two but such that water solutions of said mixture are characterized by sudsing and detergent power greater than that predictable from the corresponding characteristics of the respective ingredients.

2. A wetting, sudsing and detergent agent comprising a mixture of sodium alkyl sulfates derived from the higher alcohols obtainable from coconut oil, and a water-soluble salt of a true sulfonic acid corresponding to the formula in which R.COO- is the radical of a fatty acid having eight to eighteen carbon atoms, the ratio of true sulfonate to alkyl sulfonate being not greater than three to two but such that water solutions of said mixture are characterized by sudsing and detergent power greater than that predictable from the corresponding characteristics of the respective ingredients.

3. A wetting, sudsing and detergent agent comprising a mixture of sodium alkyl sulfates derived from the higher alcohols obtainable from coconut oil, and a water-soluble salt of a true sulfonic acid corresponding to the formula in which R-CO0-- is the radical of oleic acid, the ratio of true sulfonate to alkyl sulfonate being not greater than three to two but such that water solutions of said mixture are characterized by sudsing and detergent power greater than that predictable from the corresponding characteristics of the respective ingredients.

4. A wetting, sudsing and detergent agent comprising a mixture of alkali metal alkyl sulfates derived from the higher alcohols obtainable from coconut oil, and a water-soluble salt of a true sulfonic acid corresponding to the formula derived from the higher alcohols obtainable from coconut oil, and a water-soluble salt of a true sulfonic acid corresponding to the formula R-COO-CHa-CHOH-CHa-SOaI-I in which R'COO- represents the mixed acid radicals contained in coconut oil, the ratio of true sulfonate to alml sulfonate being not greater than three to two but such that water solutions of said mixture are characterized by sudsing and detergent power greater than that predictable from the corresponding characteristics of the respective ingredients.

6. The process of preparing a spray dried laundering agent, the active ingredient of which consists in part of primary alkyl sulfate having eight to eighteen carbon atoms in the alkyl radical, which comprises incorporating with two parts of the primary alkyl sulfate prior to spray drying -not more than three parts of a watersoluble salt of a true sulfonic acid corresponding to the general formula in which R denotes an aliphatic radical having eight to eighteen carbon atoms and-XR1--denotes an oxyalkylene or an amino alkylene radical, said salts being substantially non-volatile at the temperature of spray drying, whereby the sudsing and detergent power of said primary alkyl sulfate in water soiution is improved to a greater extent than that predictable from the characteristics of the true sulfonic acid salt added.

'2. The process of preparing a spray dried laundering agent, the active ingredient of which consists in part of the higher primary alkyl sulfates obtainable from coconut oil which comprises adding to and incorporating with two parts of the primary alkyl sulfate prior to spray drying not more than three parts of a water-soluble salt of a true sulfonic acid corresponding to the formula in which R,CO0- is the radical of oleic acid,

whereby the sudsing and detergent power of said primary allq'l sulfate is improved to a greater extent than that predictable from the characteristics of the true sulfonic acid salt added.

8. The process of preparing a spray dried laundering agent, the active ingredient of which consists in part of the higher primary alkyl sulfates obtainable from coconut oil which comprises adding to and incorporating with two parts of the primary alkyl sulfate prior to spray drying not more than three parts of a water-soluble salt of a true sulfonic acid corresponding to the formula R-CO-N-CaHc-SOaH in which R,- is the alkyl radical contained in oleic acid, whereby the sudsing and detergent power of said primary alkyl sulfate is improved to a greater extent than that predictable from r the characteristics of the true sulfonic acid salt added.

9. The process of preparing a spray dried laundering agent, the active ingredient of which consists in part of the higher primary alkyl sulfates obtainable from coconut oil which comprises adding to and incorporating with two parts of the primary alkyl sulfate prior to spray drying not more than three parts of a water-soluble salt of a true sulfonic acid corresponding to the formula in which R-COO- represents the mixed acid radicals contained in coconut oil, whereby the sudsing and detergent power of said primary alkyl sulfate is improved to a greater extent than that predictable from. the characteristics of the true sulfonic acid salt added.

10. A detergent preparation having greater sudsing power in water solution from that predictable from the corresponding characteristics of the respective ingredients and containing as the active detergent a mixture consisting essentially of about 70-95 per cent of the sodium salt of alkyl sulfuric acids obtained by the sulfation of the higher alcohols derived from coconut oil and about 5-30 per cent of the sodium salt of the true sulfonic acid corresponding to the general formula in which R.- is the alkyl radical contained in oleic acid.

11. A detergent preparation having greater sudsing power in water solution than that predictable from the corresponding characteristics of the respective ingredients and containing as the active detergent a sudsing mixture consisting essentially of about 70-95 per cent of the sodium salt of alkyl sulfuric acids obtained by the sulfation of the higher alcohols derived from coconut oil and about 5-30 per cent of the ammonium salt of a true sulfonic acid corresponding to the general formula in which R-COO is the radical of oleic acid.

12. A detergent preparation having greater sudsing power in water solution than that predictable from the corresponding characteristics of the respective ingredients and containing as the active detergent a mixture consisting essentially of about 70-95 per cent of the sodium salt of alkyl sulfuric acids obtained by the sulfation of the higher alcohols derived from coconut oil and about 5-30 per cent of the sodium salt of the true sulfonic acid corresponding to the general formula in which R-COO represents the mixed acid radicals contained in coconut oil.

13. A detergent composition containing as the active constituent a mixture consisting essentially of about seventy per cent to about ninety-five RCO- -X--R1SOaH in which R denotes an aliphatic radical having eight to eighteen carbon atoms and -X?-R1 denotes an oxyaikylene or an amino alkylene radical, said composition having greater detergent and lathering power in water solution than that predictable from the corresponding characteristics of the respective constituents. W

WILFRED S. MARTIN.

DISCLAIMER 2,156,996.W'ilfred S. Martin, Norwood, Ohio. Patent dated May 2, 1939. the assignee, The Procter ch Gamble Company.

and 6 wetting,

POSITIONS.

Hereby disclaims from claims 1 DETERGENT AND WETTING 00M- Disclaimer filed June 4, 1940, by

sudsing and detergent agents other than those in which the alkyl sulfates of the mixture are obtained by reaction of the sulfating agent on higher molecular weight normal primary aliphatic alcohols.

[Oflicial Gazette July 2, 1.940.] 

